WO2021173683A1 - Mise en forme de plasma pour la croissance de diamant - Google Patents

Mise en forme de plasma pour la croissance de diamant Download PDF

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Publication number
WO2021173683A1
WO2021173683A1 PCT/US2021/019431 US2021019431W WO2021173683A1 WO 2021173683 A1 WO2021173683 A1 WO 2021173683A1 US 2021019431 W US2021019431 W US 2021019431W WO 2021173683 A1 WO2021173683 A1 WO 2021173683A1
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WIPO (PCT)
Prior art keywords
plasma
plasma plume
chamber
plume
shape
Prior art date
Application number
PCT/US2021/019431
Other languages
English (en)
Inventor
John P. CIRALDO
Jonathan LEVINE-MILES
Original Assignee
J2 Materials, Llc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by J2 Materials, Llc filed Critical J2 Materials, Llc
Priority to EP21761398.3A priority Critical patent/EP4110977A4/fr
Priority to AU2021225841A priority patent/AU2021225841A1/en
Priority to CA3173037A priority patent/CA3173037A1/fr
Priority to CN202180028675.5A priority patent/CN115605638A/zh
Priority to IL295784A priority patent/IL295784A/en
Priority to JP2022551039A priority patent/JP2023515564A/ja
Publication of WO2021173683A1 publication Critical patent/WO2021173683A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C23C16/27—Diamond only
    • C23C16/274—Diamond only using microwave discharges
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/511—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using microwave discharges
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C30B25/10—Heating of the reaction chamber or the substrate
    • C30B25/105—Heating of the reaction chamber or the substrate by irradiation or electric discharge
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements
    • C30B29/04—Diamond

Definitions

  • Illustrative embodiments of the invention generally relate to formation of diamonds on substrates and, more particularly, the illustrative embodiments of the invention relate to plasma shaping for targeted diamond growth.
  • Diamonds are used in a wide variety of applications. For example, they can be used for producing integrated circuits, or as lenses for laser systems. They also can be used simply as gemstones. Fabricating diamonds, however, can produce a number of technical challenges.
  • Chemical vapor deposition is a process in which films of materials are deposited from the vapor phase by the decomposition of chemicals on the surface of a substrate. Most frequently the process is thermally driven but photo- and plasma-assisted methods are also used. The deposition of the film is controlled by a chemical reaction.
  • a system grows diamonds.
  • the system includes a chemical vapor deposition reactor having a microwave chamber.
  • the system further includes a single-crystal seed configured to be positioned in the chamber.
  • the system also includes a precursor gas.
  • a microwave source is configured to energize the precursor gas to produce a plasma plume.
  • An electromagnetic source of the system is configured to generate a steering field to adjust a position of the plasma plume in the chamber and/ or to adjust a shape of the plasma plume.
  • the microwave source emits microwave radiation.
  • the microwave source may produce a first electric field that energizes the gas.
  • the electrically charged gas may include methane and hydrogen.
  • the first electric field and the steering field may be at least partially superposed.
  • the electromagnetic source may include, among other things, a magnetic coil, an electrically charged ring, and/ or an electrically biased mechanical support.
  • the system may further include a mechanical support on which the single-crystal seed is positioned.
  • the system may further include a plurality of single-crystal seeds formed from diamond.
  • the system may include a deposition feedback system.
  • the deposition feedback system is configured to determine a temperature of one or more seeds, measure a dimension of one or more grown diamonds, and/ or determine a shape of the plasma plume. As a result of the deposition feedback, the field strength and/ or other property of one or more electromagnetic sources may be adjusted.
  • a method generates a plasma plume in a chamber.
  • the chamber is configured so that the plasma plume is unstable or metastable. Accordingly, the plasma plume moves between a first position and a second position.
  • the method biases the plasma plume towards the first position.
  • the method may also provide a single-crystal seed in the chamber.
  • the chamber may be a cylindrical chamber. Carbon from the plasma plume is deposited, through a series of reactions, onto the single-crystal seed to form diamond.
  • the single-crystal seed is positioned on a mechanical support. In some chambers, the first position is above the single crystal seed, and the second position is at a top of the chamber. However, other positions are of the plasma plume are possible.
  • the method may generate an electric field for biasing the plasma plume. Additionally, or alternatively, the method may generate a magnetic field for biasing the plasma plume. Some embodiments generate a second magnetic field or second electric field to modify the shape of the biased plasma plume.
  • a method controls diamond growth.
  • the method provides a single-crystal seed in a growth environment.
  • a gas containing carbon is energized to produce a plasma plume.
  • the method creates steering fields to modulate the deposition characteristics of the plasma plume.
  • the steering fields are configured to change the shape of the plasma plume.
  • the method changes the shape of a boundary of the plasma plume facing the seed to have a larger radius of curvature. Additionally, or alternatively, the method may increase the deposition area by changing the shape of the plasma plume to be wider.
  • the steering fields may be generated by using one or more magnetic fields, electric fields, and/ or electromagnetic fields.
  • a position and/ or shape of a plasma plume used to grow diamond The method provides a single crystal seed in a growth environment. The single-crystal seed is formed from diamond.
  • the method energizes a gas containing carbon to produce a plasma plume that deposits free carbon atoms onto the single-crystal seed.
  • the method also creates steering fields to modulate the carbon atom deposition characteristics of the plasma plume.
  • the growth environment is within a chemical vapor deposition chamber.
  • the gas may include methane.
  • the carbon atom deposition characteristics of the plasma plume may be modulated by reshaping the plasma plume and/ or changing a density of at least a portion of the plasma plume.
  • the steering fields may change the shape and/ or density of the plasma plume.
  • the steering fields may change the shape of a portion of the plasma plume facing the seed to have a larger radius of curvature (i.e., become more planar).
  • the steering fields may increase deposition area by changing the shape of the plasma plume to be wider.
  • the steering fields may be created by one or more magnetic fields, electric fields, and/ or electromagnetic fields.
  • the steering fields may be created by one or more permanent magnets.
  • the magnets may be positioned adjacent to the deposition area.
  • the steering fields may be created using one or more electromagnetic coils.
  • the electromagnetic coil may envelop the deposition area and/ or the chamber.
  • the steering fields may also be created via an electrically (voltage) biased ring or plate.
  • the electromagnetic coils are positioned adjacent to the seed and/ or external to the chamber, producing an inductively coupled plasma.
  • Figure 1 schematically shows a diamond growth environment at the beginning of the diamond growth process in accordance with illustrative embodiments of the invention.
  • Figure 2 schematically shows diamond growth in the diamond growth environment in accordance with illustrative embodiments of the invention.
  • FIGS 3A-3G schematically show modulation of the plasma plume using different types of electric, magnetic, and/ or electromagnetic fields in accordance with illustrative embodiments of the invention.
  • Figure 4 shows a process of growing diamonds in accordance with one exemplary embodiment of the invention.
  • Illustrative embodiments adjust a position and/ or shape of a plasma plume to improve deposition of diamond using chemical vapor deposition.
  • illustrative embodiments use microwave plasma chemical vapor deposition.
  • the plasma plume has a shape defined largely by the distribution of ions within the plume.
  • the plume has a predictable shape and position inside of the CVD chamber.
  • Illustrative embodiments use magnetic fields and/ or electric fields to advantageously modulate the position and/ or shape of the plume.
  • Figure 1 schematically shows a diamond growth environment 10 in accordance with illustrative embodiments of the invention.
  • the growth environment 10 is the inside of a chamber 15 used for chemical vapor deposition (CVD).
  • CVD chemical vapor deposition
  • a plasma 16 (also referred to as a plasma plume 16) is produced by ionizing gas 32 (e.g., using microwaves 30 to energize methane).
  • the gas 32 may be injected into the chamber 15, and may include, among other things, various concentrations of hydrogen, methane, argon, nitrogen, and/ or oxygen.
  • a refractory metal support 11 Inside the chamber 15 are one or more diamond seeds 12 arranged (e.g., directly) on a refractory metal support 11.
  • the refractory metal support 11 may itself be positioned on a temperature controlled growth stage 13.
  • the diamond seeds 12 may be positioned directly on the growth stage 13.
  • the chamber 15 is filled with the gas 32 precursors that are formed into the hot plasma 16.
  • the plasma 16 may be formed by energizing (e.g., by using microwaves 30) the electrically charged gas 32, such as methane (CTL t ).
  • CTL t the electrically charged gas 32
  • the inventors believe that when the plasma 16 is energized, the gas 32 atoms break apart, allowing the free carbon atoms to attach to the seed 12 crystals through a series of reactions. Accordingly, diamond 14 (or other crystal 14) growth occurs at a growth interface 26.
  • FIG 2 schematically shows diamond 14 growth in the diamond growth environment 10 in accordance with illustrative embodiments of the invention.
  • the position and/ or orientation of the diamond growth interface 26 with respect to the plasma plume 16 impacts the growth of diamonds 14 via CVD.
  • the diamond growth interface 26 is the exposed surface of the diamond seed 12.
  • the diamond growth interface 26 includes a surface defined by new diamond 14 growth.
  • the plasma plume 16 provides both free radicals and thermal energy for the deposition process. Therefore, the position of the plume 16 with respect to the diamond growth interface 26 (e.g., the diamond seed 12) is a concern for growth mechanisms.
  • the plume 16 does not have a well-defined boundary, and therefore an exact shape, it is typical to treat the plasma 16 as having a shape for simplicity of discussion. For example, it is possible to visualize the shape of the plasma plume 16 as the area of intense optical emission.
  • the plume 16 tends to be rounded near the growth interface 26, which can make it difficult to maintain uniform growth conditions when growing multiple diamonds 14 simultaneously (e.g., as shown in Figure 2).
  • the individual diamonds 14 are typically aligned along a single plane (e.g., defined by the seeds 12), while the plasma 16 shape (e.g., the portion of the plume 16 closest to the growth interface 26) is inherently non-planar.
  • the diamond seed 12A is further away from the "boundary" of the plasma plume 16 than the diamond seed 12B.
  • the boundary 34 can be said to include some or all of the plasma plume 16 portion that faces the growth interface 26.
  • This difference in distance from the boundary 34 of the plume 16 causes differences in temperatures and growth conditions of various seeds 12 (e.g., seed 12B towards the middle as compared to the seed 12A towards the edge). Accordingly, as shown in Figure 2, diamond 14 growth may be non-uniform on seed 12A as compared to the seed 12B.
  • the results of the inhomogeneous growth conditions that arise from the non-planar shape of the plasma plume 16 include large thermal gradients across the growing diamonds 14. These inhomogeneous growth conditions are caused by thermal gradients across the growing diamonds 14 (i.e., from the plasma 16 itself), as well as varying growth conditions due to the various parts of the growth interface 26 being at different distances from the plasma plume 16 (e.g., the boundary 34).
  • Illustrative embodiments may modify the plasma 16 shape during growth, including by optimization of procedure and/ or injection of inert gaseous species, both of which may alter the kinetics within the plasma plume 16. As discussed below, these techniques can modify the shape of the plume 16. The inventors discovered that active measures may be utilized to modify the shape or position of the plasma 16 in-situ without the need for significant modifications to the process conditions, such as pressure, temperature or gas chemistry.
  • the modifications to the plume 16 may include, for example, making the plume 16 denser in targeted areas, modifying the boundary 34 of the plume 16 to correspond to the shape of the growth interface 26 (e.g., to normalize distance between boundary 34 and growth interface 26), and/ or making the boundary 34 substantially planner. These various modifications may improve growth kinetics and, ultimately, growth rate and final qualify of diamond 14 material. As another example, the plume 16 may be broadened, allowing for increased deposition area. Accordingly, grown diamond 14 quantify and qualify may be improved.
  • FIGS 3A-3C schematically show various techniques for reshaping and/ or repositioning the plasma plume 16 in accordance with illustrative embodiments of the invention.
  • the plasma plume 16 can be shaped (also referred to as steered) using electric and/ or magnetic fields. These techniques allow for the plasma 16 to be actively reshaped into a reshaped plasma 16A (e.g., including reshaped boundary 34A) by the field (optionally without modifications to process conditions, including pressure and gas chemistry).
  • the growth environment 10 can be made more homogenous, reducing growth variabilities and instabilities. Additionally, the plasma 16 may be made denser in the area of interest, improving growth kinetics and, ultimately, growth rate and final quality of the grown diamond 14 material.
  • the plume 16 may be broadened such that the reshaped boundary 16A can be considered substantially planar (e.g., the plasma plume 16A has a large radius of curvature facing the diamond growth interface 26).
  • the plasma 16 may be said to have a radius of curvature at the boundary 34. Illustrative embodiments may shape the plume 16A to increase the radius of curvature, thereby making the boundary 34A less rounded and more planar.
  • Illustrative embodiments advantageously modify the plasma plume 16 so that the crystals 14A grown near the edge of the growth interface 26 experience substantially the same growth conditions as crystals 14C grown near the center. Without modification of the plume 16, the crystal 14A near the edge sees a different chemistry and temperature from the crystal 14C near the center.
  • some embodiments may have a plume 16 that provides substantially homogenous growth conditions for a 3x3 arrangement of seeds 12 (e.g., to grow 9 crystals 14).
  • Some embodiments may adjust the shape of the plume 16 such that a 4x4 arrangement of seeds 12 can grow homogeneously (i.e., 16 crystals 14). Accordingly, illustrative embodiments advantageously enable near 2x, or greater than 2x, growth of the number of homogeneous crystals 14 for an otherwise identical growth environment 10. Furthermore, the plume 16 can be flattened (i.e., made substantially planar at the boundary 34 or portions thereof) such that seed crystals 12 may have homogeneous growth conditions in a 5x5 arrangement. Some embodiments enable homogeneous growth of seed 12 arrangements that are greater than 5x5 (e.g., up to 10x10).
  • 5x5 e.g., up to 10x10
  • the shape of the boundary 34 of the plume 16 substantially corresponds to the shape of the growth interface 26. While exact correspondence of shape is desirable, one of skill in the art understands that even minor improvements in the correspondence of the shape of the plume 16 (e.g., the boundary 34) with the shape of the growth interface 26 may provide various advantages described herein.
  • the seeds 12 are positioned on support 11 and/ or stage 13, which are substantially planar.
  • Illustrative embodiments may modify the shape of the plume 16 to be substantially planar (i.e., correspond to the shape of the growth interface 26 which is also substantially planar). It should be understood that while the growth interface 26 may have discontinuities (e.g., between seeds 12), or a minor angular miscut on the seeds 12 and/ or diamonds 14, that the growth interface 26 may still be considered to be substantially planar. It is unlikely that the shape of the plume 16 corresponds exactly to the shape of the growth interface 26.
  • illustrative embodiments may use a magnetic field and/ or an electric field.
  • the inventors have found that both types of fields are capable of adjusting the shape of the plume 16. This is because the plasma plume 16 is similar to a gas that is electrically conductive, which is highly responsive to electric fields. Because the ions of the plasma 16 are in motion, the shape of the plume 16 is also responsive to magnetic fields. Accordingly, illustrative embodiments may use magnetic and/ or electric fields to steer a charged particle, and thereby adjust the shape of the plume 16.
  • the magnetic and/ or electric bias may be applied to the seeds 12 and/ or to the plume 16.
  • various portions of the plume 16 may be charged (e.g., the outer edge of the plume 16 may be steered down without steering the center of the plume 16 down).
  • the steering field when the steering field is magnetic in nature, it may include one or more electromagnetic source, such as permanent magnets 20 (e.g., rare earth magnets 20), that are positioned adjacent to the deposition area (e.g., adjacent to the growth interface 26).
  • the field may be produced by one or more electromagnetic source such as electromagnetic coils 22.
  • the magnetic coils 22 may be positioned, for example, external to the chamber 15 to produce an inductively coupled plasma 16A (e.g., wrapped around the chamber 15). Alternatively, or additionally, the magnetic coils 22 may built into the walls of the chamber 15.
  • Figure 3C schematically shows an electromagnetic coil 22 surrounding the chamber 15 in accordance with illustrative embodiments of the invention.
  • the electric and/ or magnetic steering fields provide better plasma 16 uniformity.
  • illustrative embodiments may also provide better process stability in certain types of reactors.
  • the plasma 16 may have a tendency to move (e.g., between two stable positions).
  • Figure 3D schematically shows two different positions 161 and 162 of the plasma plume 16 within the chamber 15 in accordance with illustrative embodiments of the invention.
  • walls 62 of the chamber 15 are shown.
  • a quartz window 60 through which a microwave source 64 emits microwave radiation 30 is also shown.
  • a gas injector 66 configured to input gas 32 into the chamber 15 is shown.
  • the walls 62, the window 60, the microwave source 64, and the gas injector 66 are not shown in other figures, it should be understood by one of skill in the art that all of these components may be present throughout the other figures. However, these components are emitted from various drawings.
  • shape, arrangement, and position of the walls 62, window 60, microwave radiation source 64, and gas injector 66 are merely illustrative, and not intended to limit various embodiments.
  • the chamber 15 is a standing wave chamber 15, which has high reflectivity to microwaves.
  • the wave bounces within the chamber with relatively low loss.
  • illustrative embodiments do not have an electrode (as compared to plasma enhanced CVD, which has an RF electrode).
  • the shape of the plasma of a system having an RF electrode is defined by the electrode.
  • the shape of the plasma 16 in a microwave chamber 15 is defined by the standing wave.
  • the stage on which the samples (e.g., substrates) are positioned is generally not biased.
  • microwave fields advantageously provide enhanced diamond growth. While diamond 14 grows in an RF field, the growth rate may be an order of magnitude lower. Disadvantageously, the plasma plume
  • illustrative embodiments advantageously adjust the size and/ or shape of the plasma 16 using a second field (e.g., electric, magnetic, and/ or electromagnetic), thereby improving growth quality and/ or the number of diamond 14 grown.
  • a second field e.g., electric, magnetic, and/ or electromagnetic
  • the plasma 16 is struck by energizing the gas 32 in the chamber 15 (e.g., by emitting microwave radiation 30 from the microwave source 64 through the quartz window 60). Because microwaves 30 are electromagnetic waves, they produce a first electric field configured to convert the gas 32 into the plasma 16. Thereafter, as known by those of skill in the art, the microwave radiation 30 continues to be emitted during the growth process to maintain the plasma 16. After the plasma 16 is struck, it generally settles in a position 161. However, the position 161 of the plasma 16 may be unstable or metastable, and the plasma 16 may move to a second position 162 (e.g., at the top of the chamber 15 bounded by the quartz window 60). In illustrative embodiments, the first position 161 may be more desirable for diamond 14 growth than the second position 162.
  • the plasma 16 when it is energized, it may have one or more stable and/ or unstable resting positions (e.g., depending on the design of the chamber 15). If both positions are unstable or metastable, then the plasma 16 may move between the first position 161 and the second position 162 over time.
  • the locations of the first position 161 and the second position 162 are a function of the shape of the chamber 15.
  • some chambers 15 are designed such that they have a single stable position 161 at which the plasma plume 16 rests, and other chambers 15 may have two or more positions 161, 162 that the plasma plume 16 moves between.
  • some chambers 16 may have symmetrical positions (e.g., the first position 161 is at above the platform 11, and the second position 162 is above the first position 161 at the top of the chamber 15).
  • the inventors have found that cylindrical chambers 15 tend to have the second position 162 at the top of the chamber (e.g., bounded by a quartz window 60 through which the microwave radiation 30 enters the chamber 15).
  • the plume 16 is at the first position 161, and a certain probability that the plume 16 is at the second position 162. Furthermore, there may also be decreasing probabilities that the plume 16 may also be at other positions. Illustrative embodiments may use the steering fields described herein to bias the plasma plume 16 towards a single stable position, advantageously increasing the probability that the plasma plume 16 is in the desired position 161.
  • Illustrative embodiments may activate a second electric field or a first magnetic field (referred to as a positioning field) before, during, and/ or after striking the plasma 16.
  • the positioning field electrically and/ or magnetically biases the plasma 16 to a particular position 161 or 162.
  • this allows control of the position of the plasma 16 which can ignite in different positions 161 or 162.
  • the plasma 16 can move to the second unstable or metastable position 162 after striking.
  • the plasma 16 may grow diamond 14 in a desirable position 161, but can destroy portions of the chamber 15 in an undesired position 162.
  • illustrative embodiments use positioning fields (e.g., generated by an electrical bias from ring 24 or a magnetic bias from coil 22) to position the plasma plume 16 in a first diamond 14 growth position 161.
  • positioning fields e.g., generated by an electrical bias from ring 24 or a magnetic bias from coil 22
  • some embodiments provide a superposition of electric fields and/ or magnetic fields (e.g., a first electric field to ignite the plasma and a first magnetic field to position the plasma).
  • the size and shape of the chamber 15 impacts the stable positions of the plume 16.
  • discussion of the impact of the size and shape of the chamber 15 on the stability and tendency of the plume 16 to move is beyond the scope of this discussion.
  • RF engineers design the chambers 15 to be resonant cavities.
  • Two well-known chamber designs commonly employed in CVD include the clam shell chamber 15 and a cylindrical chamber 15. The inventors have found that the clam shell chamber 15 tends to have a single stable position 161, while the cylindrical chamber 15 tends to cause the plume 16 to move between at least two positions 161 and 162.
  • FIG 3E schematically shows the chamber 15 configuration of Figure 3C with the plume 16 biased in the first position 161.
  • the plasma 16 may be inductively coupled by positioning the electromagnetic coil 22 around the perimeter of the chamber 15.
  • the coil 22 produces a positioning field inside of it that is laminar and parallel to the coil 22.
  • the produced electrical field inside of the coil 22 is uniform and points in a single direction.
  • the coil 22 biases the plume 16 either up or down, depending on the direction of the current.
  • the coil 22 may be used to bias the plume 16 in its first position 161 in addition to, or as an alternative to, changing the shape of the plume 16.
  • the metal stage 11 creates a boundary condition for the plasma 16 by creating a repulsive force when the metal stage 11 is electrically charged.
  • the closer the plasma 16 is pushed towards the stage the more the electromagnetic force pushes the plasma 16 away. Accordingly, the center of the plasma 16 can be repelled by the stage 11, while the edges of the plasma 16 may get pushed down.
  • Figure 3F schematically shows an alternative arrangement for biasing the plume 16 in the first position 161 in accordance with illustrative embodiments.
  • a ring 24 may be positioned around the outside of the diamond 14 growth area and/ or growth interface 26.
  • the ring 24 may be electrically biased.
  • the ring 24 is shown at a height lower than the deposition surface. However, in some embodiments, the ring may be at the same height as the deposition surface.
  • the entire ring 24 may be biased.
  • illustrative embodiments may produce local bias points, for example, under each of many individual seeds, in order to compensate for physical variabilities, such as height differentials, between the individual seeds.
  • the edges 16B of the plume 16 may be pulled downwards without steering the center 16C downwards.
  • Illustrative embodiments position the ring 24 around the growth so that it is closer to the outer edges 16B of the plume than the center 16C.
  • a variety of dimensions and positions may be used for the ring 24.
  • field strength is proportional to 1/ r 2 .
  • the outside edge 16B (which is closer to the ring 24) experiences a greater steering force relative to the center 16C of the plume 16.
  • the plasma 16 is thus steered to flatten out at the edges 16B while having very little impact on the center 16C of the plasma 16 (e.g., as shown in steered plasma 16A).
  • Figure 3G shows yet another embodiment for biasing the plume 16 into a desired position and/ or shape in accordance with illustrative embodiments of the invention.
  • the stage 11 itself is electrically biased (e.g., by applying a voltage to the stage 11).
  • the steering forces produced by the bias plate are used to steer the plasma into a desired shape and/ or position.
  • the stage can be biased in targeted locations.
  • the bias can occur at the position of each of the seeds 12.
  • the seeds 12 can be arranged spaced out from each other around the stage 11, and each seed 12 can be biased independently.
  • Such a biasing configuration provides greater specificity for steering the plasma 16 (e.g., where the plasma 16 should go and where you don't want the plasma 16 to go). This can be particularly advantageous in situations where the seeds 12 don't always grow at the same rate.
  • the seed 12 having reduced growth may draw more plasma 16 towards it.
  • the seed 12 experiencing faster growth may stop or reduce the amount of plasma 16 that is steered towards it.
  • one or more seeds may be biased to push plasma 16 further away, while other seeds 12 attract plasma 16.
  • Some embodiments may include temperature sensors configured to detect the temperature at each seed 12.
  • each seed 12 may be on a discrete pad that may have a unique voltage applied thereto.
  • Each pad may also have a discrete temperature sensor.
  • the pads likely would not have sensors.
  • illustrative embodiments may measure the temperature optically, such as with a pyrometer or IR camera. In general, the closer the plasma 16 is to a particular part of the growth interface 26, the hotter the temperature is at that location. Thus, temperature feedback can be used to automatically adjust the amount of plasma 16 that is steered to a particular location.
  • the temperature of the hotter seed 12 can trigger a microcontroller to change the biasing voltage and reduce the steering of plasma towards that seed 12.
  • optical feedback may be used to adjust the steering fields.
  • a camera can image the plasma 16 and communicate with a controller that maps out the shape of plume 16 as a function of the intensity of the light.
  • the intensity of the light can be used to adjust the height of various parts of the plasma plume 16.
  • Figure 4 shows a process 400 of growing one or more diamonds in accordance with one embodiment of the invention. It should be noted that this method is substantially simplified from a longer process that may normally be used. Accordingly, the method of Figure 4 may have many other steps that those skilled in the art likely would use. In addition, some of the steps are optional (e.g., step 410) and/ or may be performed in a different order than that shown (e.g., step 406 may begin before step 404), or at the same time. Those skilled in the art therefore can modify the process as appropriate.
  • the process 400 may be executed inside a furnace, reactor, or other device (not shown) having a chamber 15 with carefully controlled environmental conditions, such as prescribed pressures, temperatures, and environmental gasses.
  • the process 400 may be carried out using the CVD method.
  • the process begins at step 402, which positions the diamond seed 12 in the growth environment 10 (e.g., inside the vacuum sealed CVD chamber 15 as shown in Figure 1).
  • the diamond seed 12 may be positioned on a refractory metal support 11, which itself may be on a temperature-controlled growth stage 13.
  • the seed 12 may be formed from, for example, magnesium oxide, iridium, silicon, yttrium-stabilized zirconium, titanium, silicon carbide, diamond, or combinations thereof. Those skilled in the art may select yet a different material for the seed 12.
  • the seed 12 has a single crystal/ monocrystalline structure.
  • the seed 12 growth surface may have a (100) crystal orientation with a miscut/ misorientation in the range of about ⁇ 5 degrees.
  • one or more diamond seeds 12 may be positioned within the chamber 15. Furthermore, although the diamond seeds 12 are shown as being aligned on a planar surface, in some embodiments, the diamond seeds 12 may be positioned differently (e.g., to match the expected "shape" of the plume 16).
  • the process then proceeds to step 404, which produces the plasma 16 (also referred to as striking the plasma 16).
  • the growth environment 10 includes the gas 32, such as methane (CFLt), which becomes a plasma 16 when it is energized 30 (e.g., by microwaves).
  • the gas 32 may be injected into the chamber 15.
  • the gas 32 may include hydrogen, methane, argon, nitrogen, and/ or oxygen.
  • the plasma 16 provides a source of carbon that is deposited onto the seeds 12 (e.g., the diamond seed 12). Accordingly, the diamond 14 growth process begins.
  • step 406 creates steering fields configured to reshape the plume 16 to guide the deposition of material from the plume 16 (e.g., a carbon containing ion) and/ or to bias the plume 16 towards a certain position.
  • illustrative embodiments may include magnets 20 (e.g., as shown in Figure 3A) or electromagnetic coils 22 (e.g., as shown in Figure 3B). While Figure 3B shows that the coil 22 envelops and/ or surrounds the deposition area, it should be understood that this is merely for illustrative purposes and not intended to limit various embodiments. Indeed, in some embodiments, the coil 22 envelops and/ or surrounds the deposition area. In some other embodiments, for example, the coil 22 may envelop the entire chamber 15 (e.g., the coil 22 may be positioned along the perimeter of the chamber 15).
  • the result is a superposition of two fields, i.e., an alternating microwave field combined with an RF or DC field.
  • the field may be produced adjacent to the deposition area, via an electrically biased ring or plate 24 having a given voltage.
  • the bias may be applied to a ring 24 that encompasses the deposition area and is positioned at a height similar to, or less than the height of the deposition surface (e.g., platen).
  • the steering fields may be used to change the shape of the plasma plume 16 (e.g., see reshaped plasma 16A in Figs. 3A-3B).
  • the plasma plume 16 may be broadened to better reach more seeds 12.
  • the shape of the plasma plume 16 may be adjusted to provide more homogenous growth characteristics.
  • the steering fields may be used to change the position of the plasma plume 16.
  • step 408 deposits diamond 14.
  • the diamond 14 deposition process may occur as the plasma plume 16 is produced.
  • the density and positioning of the deposited diamond 14 may be changed when the steering fields are created. In some embodiments, such as when permanent magnets are utilized, the fields may always be present, even when the reactor is not in use. Accordingly, the 'deposition profile' of the plume 16 is changed.
  • the process receives diamond 14 growth feedback.
  • the feedback may be relevant to a temperature of the one or more seeds 12.
  • the feedback may also be from a visual monitoring/ inspection system (e.g., a camera) that views the plasma plume 16 from the side, and determines a distance of the plume 16 to particular seeds 12. Additionally, or alternatively, an optical and/ or laser measuring system may measure the height of the grown diamond 14.
  • a visual monitoring/ inspection system e.g., a camera
  • an optical and/ or laser measuring system may measure the height of the grown diamond 14.
  • the process may return to step 406, which adjusts the steering fields on the basis of the feedback received in step 409. For example, if a particular seed 12 has a higher temperature than other seeds 12, then the system can reduce the steering forces that attract the plasma plume 16 towards that seed 12. As another example, if a particular diamond 14 has not grown as quickly as other diamonds 14, the height of the shorter diamond 14 can be used as feedback to attract the plasma plume closer to that diamond (e.g., either by pulling the plume 16 down closer to the diamond 14 and/ or widening the plume).
  • the feedback could be use to adjust the steering fields. In illustrative embodiments, the steering fields are adjusted to make the growth rate of the various diamonds 14 grown more uniform.
  • the process concludes at step 410, which post processes the diamond 14.
  • the process may polish or anneal one or both sides of the resulting diamonds 14depending on their ultimate application.
  • one side of the diamond 14 may be polished, and/ or the grown diamond 14 may be doped for some downstream application.
  • Other post-process may cut the grown bulk diamond 14 into wafers of prescribed sizes or shapes.
  • PVD Puld laser deposition
  • PLD pulsed laser deposition
  • PLD pulsed laser deposition
  • a high-power pulsed laser beam is focused inside a vacuum chamber to strike a target of the material that is to be deposited.
  • This material is vaporized from the target in a plasma plume, which deposits it as a thin film on a substrate (such as a silicon wafer facing the target).
  • a substrate such as a silicon wafer facing the target.
  • illustrative embodiments may apply to a variety of deposition types that produce a plasma plume.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Chemical Vapour Deposition (AREA)
  • Formation Of Insulating Films (AREA)

Abstract

Un système fait croître des diamants. Le système comprend un réacteur de dépôt chimique en phase vapeur ayant une chambre à micro-ondes. Le système comprend en outre un germe monocristallin conçu pour être positionné dans la chambre. Le système comprend également un gaz précurseur. Une source de micro-ondes est conçue pour exciter le gaz précurseur afin de produire un panache de plasma. Une source électromagnétique du système est conçue pour générer un champ de direction pour régler une position du panache de plasma dans la chambre et/ou pour régler une forme du panache de plasma.
PCT/US2021/019431 2020-02-24 2021-02-24 Mise en forme de plasma pour la croissance de diamant WO2021173683A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP21761398.3A EP4110977A4 (fr) 2020-02-24 2021-02-24 Mise en forme de plasma pour la croissance de diamant
AU2021225841A AU2021225841A1 (en) 2020-02-24 2021-02-24 Plasma shaping for diamond growth
CA3173037A CA3173037A1 (fr) 2020-02-24 2021-02-24 Mise en forme de plasma pour la croissance de diamant
CN202180028675.5A CN115605638A (zh) 2020-02-24 2021-02-24 用于金刚石生长的等离子体成形
IL295784A IL295784A (en) 2020-02-24 2021-02-24 Plasma design for diamond growth
JP2022551039A JP2023515564A (ja) 2020-02-24 2021-02-24 ダイヤモンド成長のためのプラズマ成形

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US62/980,673 2020-02-24

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CA (1) CA3173037A1 (fr)
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CN114231943A (zh) * 2021-12-13 2022-03-25 深圳优普莱等离子体技术有限公司 一种用于化学气相沉积的二级升降系统及设备

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US5145711A (en) * 1987-08-10 1992-09-08 Semiconductor Energy Laboratory Co., Ltd. Cyclotron resonance chemical vapor deposition method of forming a halogen-containing diamond on a substrate
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US5370912A (en) * 1988-10-31 1994-12-06 Norton Company Diamond film deposition with a microwave plasma
US5704976A (en) * 1990-07-06 1998-01-06 The United States Of America As Represented By The Secretary Of The Navy High temperature, high rate, epitaxial synthesis of diamond in a laminar plasma
US6200652B1 (en) * 1997-07-07 2001-03-13 Cvd Diamond Corporation Method for nucleation and deposition of diamond using hot-filament DC plasma
US20060018820A1 (en) * 2004-07-20 2006-01-26 Little Reginald B Magnetic stimulated nucleation of single crystal diamonds
US7883684B2 (en) * 2005-05-25 2011-02-08 Carnegie Institution Of Washington Colorless single-crystal CVD diamond at rapid growth rate
US9410242B2 (en) * 2010-12-23 2016-08-09 Element Six Technologies Limited Microwave plasma reactor for manufacturing synthetic diamond material
US20170021420A1 (en) * 2014-06-20 2017-01-26 Velo3D, Inc. Apparatuses, systems and methods for three-dimensional printing

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CN115605638A (zh) 2023-01-13
CA3173037A1 (fr) 2021-09-02
AU2021225841A1 (en) 2022-09-15
JP2023515564A (ja) 2023-04-13
IL295784A (en) 2022-10-01
US20210262117A1 (en) 2021-08-26
EP4110977A1 (fr) 2023-01-04
EP4110977A4 (fr) 2024-03-13

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